CN87102772A - But the hydrogel siccative its preparation method that contains dispersed polymeres particle of hydration and the application in biology thereof - Google Patents

But the hydrogel siccative its preparation method that contains dispersed polymeres particle of hydration and the application in biology thereof

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Publication number
CN87102772A
CN87102772A CN87102772.0A CN87102772A CN87102772A CN 87102772 A CN87102772 A CN 87102772A CN 87102772 A CN87102772 A CN 87102772A CN 87102772 A CN87102772 A CN 87102772A
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siccative
polymkeric substance
water
substance
acid
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CN1008910B (en
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多米尼克·真尔梅
让·克洛德达尼埃尔
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/291—Gel sorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/12—Agar or agar-agar, i.e. mixture of agarose and agaropectin; Derivatives thereof
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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/916—Hydrogel compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/902—Core-shell

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Abstract

The present invention is but that to contain a kind of hydrated hydrogel siccative of the softening agent at the macromolecular substance A that can form porous aquagel in the presence of the water, a kind of water-soluble linear polymer B, a kind of above-mentioned macromolecular substance A and the polymkeric substance C that is made by a kind of water-fast monomer is at least arranged be that the particles dispersed on basis is in above-mentioned matrix.The aqueous solution of A is mixed mutually with polymer B, softening agent and polymkeric substance C latex, but then hydrogel moulding and the drying that obtains made the hydration siccative.This siccative can be used for biology after the hydration once more.

Description

But the hydrogel siccative its preparation method that contains dispersed polymeres particle of hydration and the application in biology thereof
But the objective of the invention is to introduce a kind of hydrogel siccative that contains dispersed polymeres particle of hydration, its preparation method and the application in biology (diagnostic test, cell cultures, affinity chromatography etc.).
Europe application for patent 87.786 has been introduced the bead of the agarose hydrated gel matrix that comprises the microballoon that contains a kind of polyacetals (for example polyacrolein) or powder, these beads can be made various uses, as affinity chromatography, blood transfusion, ion exchange resin, diagnostic test etc.
There are some shortcomings in use in these products: the polyacrolein difficulty is synthetic and monomer is poisonous, and in addition, these beads are in unworkable wet gel state.
The French Patent of having published 2,297,879 has been narrated the preparation method of the dry plate of the hydration again that contains agarose or Polygalactan, and it is technical that these dry plates can be used for immunodiffusion(ID), electrophoresis etc.; Described method is included in to form on a kind of carrier and contains the agarose of water-soluble polyacrylamide or the aquagel membrane of Polygalactan, then with the gel-film drying.
The advantage of these thin slices is energy prolonged preservation, hydration again when needing; But these thin slice purposes are limited.
Same known on the aqueous dispersion polymerization composition granule fixing protein, when use granules of polystyrene, adopt absorption process, perhaps when usefulness has the polymkeric substance of active group, use covalent method.The advantage that latex presents is because particle performance goes out the big and utilizable chemical property wide ranges of specific surface.On the contrary, their shortcoming is the colloid instability, particularly for ionogen, and the fixing particle of wanting isolating material above being difficult to be recovered in.
Applicant of the present invention has invented a kind of by the substrate composed siccative that can generate porous gel in the presence of water, and the polymer beads of being made by a kind of water-fast monomer is dispersed in the matrix; The advantage of this product is an easy handling, and purposes is wide.
But the present invention relates to the hydrated hydrogel siccative be characterised in that comprising:
-a kind of matrix is made up of the macromolecular substance A that can generate porous aquagel in the presence of water
-a kind of water miscible simple linear polymer B
The softening agent of-a kind of above-mentioned macromolecular substance A
-being dispersed in the particle in the above-mentioned matrix based on polymkeric substance C, polymkeric substance C is at least by a kind of water-fast monomer derived, and its second-order transition temperature surpasses 30 ℃ (preferably above 60 ℃) and may have some active function groups.
The hydratable siccative shape that the object of the invention relates to can be arbitrarily: film, plate, rod, ingot, ball etc.
The macromolecular substance A that forms matrix can be by selection in polysaccharide, the protein etc., and the aqueous solution of these materials can generate a kind of gel when being cooled to 30 to 80 ℃.
The example of poly-gala carbohydrate such as agarose or Polygalactan, pectin, protein such as gelatin, collagen protein.
The water-soluble linear polymer B that exists in product of the present invention can be by 22 ℃ of following its 5%(weight) solution viscosity be lower than in the water-soluble polymers of 17,000 centipoises (being preferably lower than 6,000 centipoises) and select.
For example, they can be polyoxyethylene glycol, polyvinyl alcohol, poly-(vinyl pyrrolidone), hydroxy alkyl cellulose, carboxyalkyl cellulose and particularly linear polypropylene acid amides.
Polyacrylamide refers to the type homopolymer of acrylamide and the linear copolymers of acrylamide and another kind of at least vinyl pyrrolidone, acrylate or methacrylic ester such as monomethyl vinylformic acid glycol ester or single vinylformic acid glycol ester comonomer equally.
In hydratable siccative, the quantity of water-soluble linear polymer B is approximately 2 to 10 times of matrix weight.
In the softening agent of macromolecular substance A, can exemplify polyalcohols such as ethylene glycol, glycerol, sorbyl alcohol, weight average molecular weight is lower than 400 polyoxyethylene glycol.
The quantity of softening agent is equivalent to 1-3 times of matrix weight approximately.
Dispersive is 0.05 to 20 micron based on the grain graininess of polymkeric substance C in matrix, best 0.1 to 3 micron.
The particle weight of using is equivalent to about 0.1 to 20 times (best about 1 to 10 times) of matrix weight.
At least make above-mentioned polymkeric substance C by a kind of water-fast unsaturated monomer.
The meaning of " water-fast monomer " is meant that solubleness is lower than 5%(weight in water) monomer.
Wherein can exemplify:
-vinyl aromatic monomer class (vinylbenzene, Vinyl toluene etc.)
The alkyl esters of-alpha-beta unsaturated acid (acrylate and methyl methacrylate, Jia Jibingxisuanyizhi etc.)
-unsaturated carboxylate type (ethyl acetate etc.)
-vinylchlorid, vinylidene chloride
-dienes (divinyl etc.)
-have a compound (vinyl cyanide etc.) of nitrile functionality
-siloxanes.
First kind of version that the object of the invention product is formed be polymkeric substance C by at least a water-fast monomer with compare with whole monomer weights, be no more than 10%(weight), preferably be no more than 4%(weight) one or more bands can Ionized group or active group for example-SO 3H ,-OSO 3H, ,-COOH, OH, NH 2,-NR 2,
Figure 87102772_IMG2
,-φ CH 2Cl ,-CONH 2Deng the comonomer multipolymer that sets out and make.
R represents C 1-C 4, C preferably 1-C 2Alkyl
For example :-vinylbenzenesulfonic acid ester, unsaturated acid sulfoalkyl ester (2-sulfoethyl methacrylic ester etc.)
-unsaturated carboxylic acid (vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid etc.)
-acrylic acid hydroxy alkyl ester or methacrylic ester (Hydroxyethyl acrylate, Propylene glycol monoacrylate etc.)
-unsaturated acid aminoalkyl ester class (methacrylic acid 2-amino ethyl ester etc.)
-acrylamide
-vinyl chloride
-glycidyl methacrylate.
Second kind of version that the object of the invention product is formed is that polymkeric substance C is a kind of alkali-soluble or acid soluble multipolymer, and promptly when the pH value appeared as alkalescence or acidity, multipolymer can be dissolved into aqueous solution form.
These multipolymers at least by a kind of water-fast monomer and at least a and all monomer weight be in a ratio of 4-90%(weight), 10-50%(weight preferably) can anionization comonomer (under the situation of alkali-soluble copolymer) or comonomer (under the situation of solubility in acid multipolymer) copolymerization that can cationization obtain.The per-cent of comonomer changes with its hydrophilic ability certainly.
Comonomer that can anionization is unsaturated carboxylic acid such as methylene-succinic acid, toxilic acid, fumaric acid etc. for example.
The solubilization pH value of the alkali-soluble copolymer that forms is generally 6-11.
Comonomer that can cationization is for example:
1) the amides N(ω-dialkyl aminoalkyl of unsaturated carboxylic acid), molecular formula is for being:
Figure 87102772_IMG3
Wherein: R 1Be H or C 1-C 4, C preferably 1-C 2Alkyl.
R 2Be C 1-C 12, C preferably 1-C 8Alkylidene group.
R 3And R 3' be C 1-C 6, C preferably 1-C 4Alkyl, may use C 1-C 9The phenyl that alkyl replaces.
Dimethylaminomethyl-acrylamide or Methacrylamide, dimethyl aminoethyl-acrylamide or Methacrylamide etc. meet this molecular formula.
2) unsaturated amino ester, molecular formula is:
Wherein: R 1' be C 1-C 5C preferably 1-C 2Alkyl.
R 2' for containing 2 carbon atoms, preferably C at least 2-C 12C particularly 2-C 8Straight chain or sub-branched alkyl.
R 3" and R 3" " is identical or different, is C 1-C 8C preferably 1-C 6And the alkyl that can replace by hydroxyl, may be by a C 1-C 9The phenyl that alkyl replaces.At R ' 2, R 3" and R 3Contained whole carbon atom numbers should surpass 8 in " " base, more preferably greater than or equal 10.
Methacrylic acid di-t-butyl amino ethyl ester, the amino propyl ester of methacrylic acid di-t-butyl, methacrylic acid diamyl amino ethyl ester all meet this molecular formula.
The solubilization pH value of the solubility in acid multipolymer that forms is lower than 8, is preferably lower than 5.
A kind of Special Circumstances of second kind of version that product is formed are lower than 100,000 by the weight average molecular weight of the polymkeric substance C that a kind of alkali-soluble copolymer is formed, are preferably lower than 50,000.
The third version of the object of the invention product component is that polymkeric substance C is " sensitization ", this means some active substances such as antibody, antigen, medicine, enzyme etc. be fixed on the particle of polymkeric substance C (" polymkeric substance C " speech be equivalent to the above-mentioned definition that has provided and comprise two kinds of versions of above-mentioned unfolded and particularly including caustic solubility and solubility in acid polymkeric substance).
The another kind of version that but the siccative of hydration is formed in the object of the invention is that the polymkeric substance C particle that is included in the matrix is can magnetized polymer beads.
Above-mentioned can magnetized particle contain 0.5-50%(weight), the magnetic fillers of 0.5-35%, particularly 0.7-20% preferably, its size is less than 1 micron, preferably between the 0.002-0.05 micron, obviously magnetic fillers is sufficiently thin so that can be included in the polymer beads.
This magnetic fillers can be made of following material, for example:
Metal and alloy thereof are as the alloy of: iron, iron-silicon, nickel, cobalt or they and molybdenum, chromium, copper, vanadium, manganese, aluminium, titanium;
The oxide compound of iron: Fe 3O 4Perhaps pure r-Fe 2O 3Perhaps with the compound or the mixture of cobalt, manganese, zinc, barium, rare-earth oxide;
Chromium dioxide.
But the siccative of hydration can follow these steps to make in the object of the invention:
1) mix following material:
The aqueous solution of a kind of macromolecular substance A down can form porous aquagel after the cooling at 30 ℃-80 ℃, and this material is carried in 30 ℃-80 ℃ and densely just can be formed above-mentioned gel in the presence of water;
A kind of water-soluble simple linear polymer B;
The softening agent of a kind of above-mentioned macromolecular substance A;
With polymkeric substance C latex, this polymkeric substance is obtained by at least a water-fast monomer, and its second-order transition temperature surpasses 30 ℃ (preferably above 60 ℃), and may have active function groups.
2) be cooled to the aqueous gel temperature that is lower than macromolecular substance A, and moulding in the hydrogel process of cooling that obtains.
3) be lower than drying under the above-mentioned gelling temp then.
Raw material used in the mixing step is as mentioned above.
The service temperature of mixing step is higher than the temperature that forms macromolecular substance A hydrogel; The concentration of macromolecular substance is with to form such needed concentration of gel suitable in the aqueous solution.Therefore, when macromolecular substance is agarose, mixing step 0.5-2%(weight) agarose solution, temperature surpasses 40 ℃, is usually less than or equals 90 ℃.
The consumption of water-soluble simple linear polymer B is equivalent to approximately that macromolecular substance A(does) 2-10 of weight is doubly.
Plasticizer dosage is equivalent to approximately that macromolecular substance A(does) 1-3 of weight is doubly.
Water-soluble simple linear polymer B and softening agent can all be dissolved in the aqueous solution of macromolecular substance A and using, and perhaps a part is dissolved in this aqueous solution, and a part is dissolved in the polymkeric substance C latex to be used.
The latex that uses contains 5-30%(weight), 10-15%(weight preferably) polymer beads.
The latex amount of using equals the amount of polymkeric substance C, is equivalent to that macromolecular substance A(does) 0.1-20 of weight doubly, preferably be about 1-10 doubly about.
When the third version of forming according to the object of the invention product, when particle has the fixed active substance, above-mentioned active substance can be introduced in the medium or use polymkeric substance C particulate latex, directly above-mentioned substance is fixed by physical absorption or chemical covalent approach thereon, perhaps use after the hydrogel encapsulation polymkeric substance C particle of macromolecular substance A, by above-mentioned active substance being moved through macromolecular substance A gel, pass through physical absorption or covalent method indirect securement then on particle.
The group on polymer beads surface and the functional group that wants the fixed biomolecules can be carried out coupled reaction make biomolecules by Covalent Immobilization on polymer beads.
This coupled reaction can be carried out according to some known methods, for example:
Use a kind of coupler (or glutaraldehyde, water-soluble carbodiimide)
Method by the activated polymer functional group effect of diazotization, cyanogen bromide, hydrazine etc. (for example by) then with want the fixed molecular reaction.
Or the like.
When but hope obtained a kind of hydration and magnetization siccative, the polymer latex of use was that its polymer beads is can magnetized latex.
Above-mentioned latex can make with known method, for example makes by Europe patent N ° 38,730 or United States Patent (USP) N ° of 4,157,323 described methods.
The hydrogel forming operation that obtains through overcooling can be undertaken by a kind of method according to the final siccative form that hope obtains.
When the macromolecular substance that uses was agarose, cooling step is preferably in 15-25 ℃ to carry out.
In case the hydrogel moulding promptly approach under the refrigerative temperature in air-flow dry.
The mixture that the first step is obtained is poured on the sheet glass, and making it to be cooled to liquid film becomes hydrogel thin film, makes the gel of form of film, then the hydrogel demoulding is also carried out drying with stating method.
Disclosed French Patent N 2,297,879 described methods are a kind of attractive moulding and drying means.
This forming method is that the mixture that the first step obtains is poured on the thermoplastic transparent plate GEL-BOD, this plate (being produced by LKB) is placed on the sheet glass of a level, make it cooling and generate hydrogel, use by the topped water-soluble glued membrane of the impregnated regenerated cellulose thin slice of aqueous glycerin solution (by " Cellophane " of Luo Na-Rhone-Poulenc's production), again the regenerated cellulose thin slice is folded to sheet glass bottom.
Integral body is carried out air stream drying at normal temperatures then; But will there be the plastic plate and the sheet glass of the siccative of hydration to separate at last again.
It is that the premium properties of matrix and the premium properties that is made polymer beads by water-fast monomer are combined that but the hydration of the object of the invention contains the advantage of the hydrogel siccative of dispersive polymer beads.The former can become film, plate, sphere and easy handling with the porous gel hydration when needed, can be with to be rich in electrolytical water-bearing media especially compatible and can infiltrate in the high-molecular weight protein; The latter is that specific surface is big and be controllable, and there are various utilizable chemical functional groups on the surface.
Above-mentioned product application is attractive especially in biology, the porous character of macromolecular substance A gel make albumen enter in the particle of polymkeric substance C and by absorb or Covalent Immobilization in particle.Many active substances all can be fixed as antibody, antigen, medicine, enzyme etc.; Character according to above-mentioned fixed active substance, can obtain a kind of carrier of in immunoenzyme or immune radiation test, affinity chromatography, purging in vitro system, using, the carrier of the enzyme catalyst of doing to use in the biology, control medication (release medicine) system, cell cultures.
Polymkeric substance C particle in the product of the present invention is a caustic solubility or acid soluble, molecular weight low (being lower than 100000), be fixed with active substance thereon, product of the present invention is noticeable especially in affinity chromatography, if for example contain the alkali-soluble polymer particle and at the such product that is fixed with antibody on the particle when antigen mixture exists, again the antigen that is identified by antibody is fixed on the particle, and still is fixed in the above after the wash-out antigen mixture always; Improve simply that the pH value can make polymer beads dissolving and move the Ag-Ab complex compound of emitting formation by porous gel.
The caustic solubility of the polymkeric substance C of any molecular weight (perhaps solubility in acid) all can be used for the composition of drug media, and by changing change pH values simply, activeconstituents wherein can discharge.
But being the character of choose reasonable macromolecular substance A, another advantage of the hydrogel siccative that contains dispersive polymer beads and hydration of the object of the invention makes that can selectively reclaim the top is fixed with the polymkeric substance C particle of wanting isolating material, and after use, destroy macromolecular substance A, for example when being a kind of collagen, macromolecular substance A destroys macromolecular substance by enzyme liberating.
Provide explanation the present invention of following example, do not limit its protection domain.
Example 1 preparation contain 0.8 micron diameter granules of polystyrene can be rehydrated dry plate
At room temperature 8 gram linear polypropylene acid amides are dissolved in 52 and restrain in the water that contains 2 gram glycerine, its 5% viscosity in aqueous solution is about 6000 centipoises under 22 ℃.This operation continues about 48 hours.
In goods, add 48 gram ESTAPOR then
Figure 87102772_IMG5
K080 latex (latex that Luo Na-Rhone-Poulenc produces is made up of 0.8 micron polystyrene monodisperse particles) is to 41% dry extract.
In addition in the ebullient water-bath with 2 the gram agaroses be dissolved in 100 milliliters contain 2 the gram glycerine softening water in.
Two kinds of solution all reach 50 ℃, mix in order to avoid generate bubble under slowly stirring then.
A transparent plastics carrier GEL-BOND(who the mixture that obtains is poured on the sheet glass that places level is produced by LKB company) on, the layer of gel of 0.8 mm thick obtained.
Integral body is cooled to room temperature, and hydrogel is attached on the carrier.
Then multiple on aquagel membrane with " Cellophane " (being produced by Luo Na-Rhone-Poulenc) thin slice, " Cellophane " thin slice is immersed in the Glycerine-Aqueous Solution of 2% glycerine in advance.With the edge break of " Cellophane " thin slice to sheet glass bottom, under the room temperature with integral body under air-flow dry 15 hours.
To take off from sheet glass by the integral body that white xerogel film, GEL-BOND carrier and " Cellon-phane " thin slice constitute subsequently, and preserve at room temperature.
To be placed in the water by the xerogel film that carrier GEL-BOND and " Cellophane " take off, at room temperature the xerogel film just can carry out rehydrated.Again change water to remove the polyacrylamide of line style.The rehydrated gel that causes expands, and granules of polystyrene is granulation not.
The siccative specific surface that calculates with every gram siccative is 4.4 square metres.
Example 2 prepares the Carboxylated Polystyrene particulate that contains 0.3 micron diameter can rehydrated siccative
Set out by following raw materials according, press example 1 described method operation:
Agarose 3 grams
Glycerine 6 grams (3 grams+3 grams)
Polyacrylamide 6 grams
·ESTAPOR
K1-030 latex 40 grams
(the ESTAPOR K1-030 that is produced by Luo Na-Rhone-Poulenc is a kind of particulate aqueous dispersion of specified diameter of Carboxylated Polystyrene, measuring particle diameter is 0.326 ± 0.010 micron, surface C OOH functional group is than being every gram dry granular 273 microequivalents, and the ratio of dry extract is 30%)
So just obtain a kind of xerogel that can be rehydrated.
The siccative specific surface that calculates with every gram siccative is 13.2 square metres.
Every gram siccative can with the carboxyl functional group ratio be 192 microequivalents.
It is that 0.2 micron benzyl chloride base polystyrene particulate can rehydrated dry plate that example 3 preparation contains diameter
Set out by following raw materials according, press example 1 described method operation:
Agarose 1 gram
Glycerine 2 grams (1 gram+1 gram)
Polyvinyl alcohol 5 grams
(by the RHODOVIOL 4-125 of Luo Na-Rhone-Poulenc's production)
·ESTAPOR
K10-020 latex 50 grams
(ESTAPOR K10-020 latex is the benzyl chloride base polystyrene particulate aqueous dispersion of the specified diameter of Luo Na-Rhone-Poulenc's production, and recording particle diameter is 0.210 ± 0.006 micron ,-φ-CH 2The ratio of Cl functional group is every gram dry granular 200 microequivalents, and the ratio of dry extract is 10%).
Obtain like this can be rehydrated xerogel.
The specific surface that calculates siccative with every gram siccative is 11 square metres.
Every gram siccative available-φ-CH 2Cl functional group is 77 microequivalents.
There is the gel of dried forms to exist the benzyl chloride base is remained unchanged and avoids its hydrolysis.This is an important advantage, there is the problem of package stability because proved benzyl chloride base polystyrene latex, in fact in storage process, the latex pH value 7-8 of beginning can drop to 2, emits chlorion and generates the benzylalcohol base owing to there is the hydrolysis of benzyl chloride base section in the surface.
Example 4 preparations contain magnetic Carboxylated Polystyrene particulate can rehydrated dried carrier
Set out by following raw materials according, press example 1 described method operation:
Agarose 2 grams
Sorbyl alcohol 5 grams (2.5 grams+2.5 grams)
Polyvinylpyridine 4 grams
(LUVIKOL K15 is produced by BASF AG)
Latex ESTAPOR
MSI-070/25 150 grams
(latex ESTAPOR MSI-070/25 is produced by Luo Na-Rhone-Poulenc, is a kind of 25%(of containing weight) magnetite Fe 3O 4The aqueous dispersion of Carboxylated Polystyrene magnetic-particle, average diameter of particles is 0.7 micron, the dried particle carboxyl functional group ratio of every gram is 40 microequivalents, the dry extract ratio is 10%).
The dry plate that obtains is cut into 1 millimeter square.
Proved after rehydrated, can make the sheet material magnetization with the test bar magnet.
Example 5 preparations contain the alkali-soluble polymer particulate can rehydrated dry plate
Set out by following raw materials according, press example 1 described method operation:
Agarose 4 grams
Ethylene glycol 4 grams (2 grams+2 grams)
Polyacrylamide 8 grams
Caustic solubility latex 20 grams
(caustic solubility latex is that weight consists of benzene hexene/methacrylic acid/ethyl propenoate terpolymer particulate aqueous dispersion of 18/41/11, particle size is 0.15 micron, the ratio of dry extract is 38.5%, it is just soluble in water to surpass 8 this trimers from the pH value, is that 9 o'clock its 10% viscosity in aqueous solution are lower than 150 centipoises at pH).
The dry plate that obtains immerses in the water of slight alkalinity (pH9) rehydrated, and dry plate becomes in water and translucently keeps its cohesive force simultaneously and discharge in water forming the particulate polymkeric substance.
Example 6 preparation contain the solubility in acid polymer beads can be rehydrated dry plate
Set out by following raw materials according, press example 1 described method operation:
Agarose 4 grams
Ethylene glycol 4 grams (2 grams+2 grams)
Polyacrylamide 8 grams
Solubility in acid latex 20 grams
(solubility in acid latex is the aqueous dispersion that weight consists of ethyl acetate/vinylformic acid diethylamino ethyl ester copolymer pellet of 90/10, particle size is 0.15 micron, the dry extract ratio is 38%, it is just soluble in water to be lower than 3 this multipolymers from the pH value, and its viscosity in aqueous solution of 10% is to be lower than 150 centipoises at 2 o'clock at pH).
The dry plate that obtains immerses in the neutral water rehydrated, is lower than at 2 o'clock if with dilute hydrochloric acid pH value is dropped to, and rehydrated dry plate becomes and translucently keeps its cohesive force simultaneously and discharge composition particulate polymkeric substance in water.

Claims (36)

  1. But 1 hydrated hydrogel siccative, it is characterized in that comprising:
    --a kind of matrix, form by a kind of macromolecular substance A that in the presence of water, can form porous aquagel;
    --a kind of water-soluble linear polymer B;
    --some are dispersed in the above-mentioned matrix, and based on the particle of polymkeric substance C, this polymkeric substance C is made by at least a water-fast monomer, and its second-order transition temperature is higher than 30 ℃, and may have active function groups.
  2. 2, according to the siccative of claim 1; It is characterized in that macromolecular substance A is an agarose.
  3. 3,, it is characterized in that water-soluble linear polymer B is the linear polypropylene acid amides according to the siccative of claim 1 or 2.
  4. 4, according to the siccative of top any one claim, but the 2-10 that the amount that it is characterized in that the water-soluble linear polymer B that exists in the hydration siccative is equivalent to matrix weight doubly about.
  5. 5, according to the siccative of top any one claim, the softening agent that it is characterized in that macromolecular substance A is a kind of polyvalent alcohol.
  6. 6, according to the siccative of top any one claim, the 1-3 that the amount that it is characterized in that softening agent is equivalent to matrix weight doubly about.
  7. 7,, it is characterized in that polymkeric substance C second-order transition temperature is higher than 60 ℃ according to the siccative of top any one claim.
  8. 8, according to the siccative of top any one claim, it is characterized in that polymkeric substance C is made by the alkyl ester of a kind of vinyl aromatic monomer, a kind of alpha-beta unsaturated acid, a kind of esters of unsaturated carboxylic acids, vinylchlorid, vinylidene chloride, a kind of conjugated diene, a kind of unsaturated monomer or a kind of siloxanes with nitrile functionality.
  9. 9,, it is characterized in that polymkeric substance C makes by a kind of water-fast monomer with less than 10% at least a comonomer that has ionizable base or active group according to the siccative of top any one claim.
  10. 10,, it is characterized in that comonomer is divinyl benzene sulfonate, unsaturated acid sulfoalkyl ester, unsaturated carboxylic acid, acrylic acid hydroxy alkyl ester or methacrylic ester, unsaturated acid aminoalkyl ester, acrylamide, vinyl chloride, glycidyl methacrylate according to the siccative of claim 9.
  11. 11,, it is characterized in that polymkeric substance C is a kind of caustic solubility or acid soluble polymkeric substance according to the siccative of top any one claim.
  12. 12, according to the siccative of claim 11, the weight average molecular weight that it is characterized in that caustic solubility or solubility in acid polymkeric substance C is lower than 100,000 and use the activating substance sensitization.
  13. 13, according to any one siccative among the claim 1-10, the particle that it is characterized in that polymkeric substance C is can be magnetized.
  14. 14,, it is characterized in that polymkeric substance C grain graininess is the 0.05-20 micron according to the siccative of top any one claim.
  15. 15,, it is characterized in that polymkeric substance C particle weight is equivalent to about 0.1-20 times of matrix weight according to the siccative of top any one claim.
  16. But the method that 16, prepares the described hydration siccative of claim 1 is characterized in that comprising following several steps:
    1) mix following material:
    The aqueous solution of a kind of macromolecular substance A down can form porous aquagel after the cooling at 30-80 ℃, and this material is carried in 30-80 ℃ and densely just can be formed above-mentioned gel in the presence of water
    A kind of water-soluble simple linear polymer B
    The softening agent of a kind of above-mentioned macromolecular substance A
    With polymkeric substance C latex, this polymkeric substance is obtained by at least a water-fast monomer, and its second-order transition temperature surpasses 30 ℃, and may have active function groups,
    2) be cooled to the aqueous gel temperature that is lower than macromolecular substance A, and moulding in the hydrogel process of cooling that obtains,
    3) be lower than drying under the above-mentioned gelling temp then.
  17. 17,, it is characterized in that macromolecular substance A is an agarose according to the method for claim 16.
  18. 18,, it is characterized in that water miscible simple linear polymer B is a kind of linear polypropylene acid amides according to the method for claim 16 or 17.
  19. 19, according to any one method in the claim 16 to 18, the 2-10 that the consumption that it is characterized in that water-soluble linear polymer is equivalent to matrix weight doubly about.
  20. 20, according to any one method of claim 16 to 19, the softening agent that it is characterized in that macromolecular substance A is a kind of polyvalent alcohol.
  21. 21, according to any one method of claim 16 to 20, the 1-3 that the amount that it is characterized in that softening agent is equivalent to matrix weight doubly.
  22. 22, according to any one method of claim 16 to 21, the second-order transition temperature of polymkeric substance C that it is characterized in that forming latex is above 60 ℃.
  23. 23, according to any one method of claim 16 to 22, the polymkeric substance C that it is characterized in that forming latex is that alkyl ester, esters of unsaturated carboxylic acids, vinylchlorid, vinylidene chloride, conjugated diolefine, the unsaturated monomer with nitrile functionality, the siloxanes by vinyl aromatic monomer, alpha-beta unsaturated acid makes.
  24. 24, according to any one method of claim 16 to 23, it is characterized in that the polymkeric substance C that forms latex makes by a kind of water-fast monomer with by at least a comonomer with ionizable or active group less than 10%.
  25. 25,, it is characterized in that comonomer is divinyl benzene sulfonate, unsaturated acid sulfoalkyl ester, unsaturated carboxylic acid, acrylic acid hydroxy alkyl ester or methacrylic ester, unsaturated acid aminoalkyl ester, acrylamide, vinyl chloride, glycidyl methacrylate according to the method for claim 24.
  26. 26, according to any one method of claim 16 to 25, it is characterized in that polymkeric substance C latex is a kind of caustic solubility or acid soluble polymer latex.
  27. 27, according to the method for claim 26, the weight average molecular weight that it is characterized in that forming the caustic solubility of latex or solubility in acid polymkeric substance C is lower than 100,000 and use the active substance sensitization.
  28. 28, according to any one method of claim 16 to 25, the particle that it is characterized in that forming the polymkeric substance C of latex is can be magnetized.
  29. 29, according to any one method of claim 16 to 28, the polymkeric substance C grain graininess that it is characterized in that forming latex is the 0.05-20 micron.
  30. 30, according to any one method of claim 16 to 29, it is characterized in that polymkeric substance C latex contains 5-30%(weight) polymkeric substance C particle.
  31. 31, according to any one method of claim 16 to 30, it is characterized in that 0.1-20 that polymkeric substance C particulate weight is equivalent to matrix weight doubly about.
  32. But 32, make the hydration siccative of film, sheet, rod, ingot, spherical formula according to any one method of claim 16 to 31.
  33. But 33, treat to be applied to biology after the hydration according to any one hydration siccative of claim 1-15 and 32.
  34. 34,, can be used for fixedly active substance according to the application of claim 33.
  35. 35, treat to be used to form drug media after the hydration according to the siccative of claim 11.
  36. 36, treat to be used for affinity chromatography after the hydration according to the siccative of claim 12.
CN87102772A 1986-04-15 1987-04-15 But the hydrogel siccative that contains dispersed polymeres particle, its preparation method and the application in biology thereof of hydration Expired CN1008910B (en)

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FR8605347 1986-04-15
FR8605347A FR2601026B1 (en) 1986-04-15 1986-04-15 DRY MATERIAL MOISTURIZABLE IN AN AQUEOUS GEL CONTAINING PARTICLES OF DISPERSE POLYMERS, METHOD FOR ITS PREPARATION AND ITS APPLICATION IN BIOLOGY

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